Effect of carbon support on the hydrogen sorption of platinum

The hydrogen sorption of carbon-supported platinum catalysts, studied by the potentiodynamic method, differs significantly from that of unsupported platinum. The difference depends on the preparation method and on the nature of the support. Possible explanations are suggested as (i) some kind of interaction between metal and support atoms during impregnation, (ii) high dispersity (amorphous structure) and (iii) hydrogen spillover onto the carbon support.

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Pt/C, . . (I) , (II) ( ), (III) .

     

Catalytic incineration of n-hexane on Pt/Al2O3

The catalytic incineration of n-hexane over a Pt/Al₂O₃ catalyst has been studied using a fixed bed reaction. The reaction was carried out in dry air between 250 and 350 °C and at 1 atm pressure. The concentration of n-hexane was between 25 and 300 ppm. The reaction was found to be zero order in n-hexane concentration and the activation energy was found to be 21 kcal/mol. The zero order kinetics can be explained by a surface redox cycle known as Mars-van Krevelen mechanism in which the oxidation of surface Pt is the rate-controlling step.

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- Pt/Al₂O₃ . , 250–350°C 1 . - 25–300 .. - –21 /. , — , , , Pt.

     

Influence of organic reagents on alumina supported nickel catalysts. I. Preparation of catalysts

Nickel/-alumina catalysts have been prepared by a version of the impregnation technique called double impregnation. The application of different organic reagents for activation of the -Al₂O₃ support promotes the formation of nickel-aluminate and large nickel crystallites in the catalysts obtained.

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/- , . . . -Al₂O₃, -, .

     

Simplest model of self-oscillations in association reactions

The simplest scheme of association reactions is suggested, whose mathematical model permits the existence of self-oscillations.

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, .

     

Support and mixing effect of an Fe2O3 catalyst for oxidative dehydrogenation of 1-butene

The support and mixing effects of Fe₂O₃ for the activity of 1-butene oxidative dehydrogenation were examined. Alumina and titania which were able to catalyze the isomerization of butene via an allyl intermediate, stimulated remarkably the formation of butadiene from butene when they were used as support or mixing component of Fe₂O₃ catalyst. Otherwise Fe₂O₃ supported on SO ₄ ^2– ion containing Al₂O₃ or TiO₂–Al₂O₃, which catalyze the isomerization via a cationic intermediate, is almost inactive for the formation of butadiene.

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Fe₂O₃ 1-. , , , Fe₂O₃. , Fe₂O₃, Al₂O₃, SO ₄ ^–2 , TiO₂–Al₂O₃, , .

     

n-Hexane cracking over heteropoly acids, 2. Catalytic activity and thermal stability of H4SiW12O40, H6P2W18O62 and H6P2W21O71(H2O)3

The catalytic activity of three heteropoly acids has been studied in n-hexane cracking. Only H₄SiW₁₂O₄₀ does not decompose into oxides at the reaction temperature. Its acidic form is active in cracking but its dehydration leads to an inactive compound.

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-. H₄SiW₁₂O₄₀ . , .

     

Influence of the preparation method on the pore spectrum of Pt?Cr/Al2O3 and Pt?Sn/Al2O3 catalysts

It is shown that, in contrast to classical impregnation methods, in bimetallic catalyst production the texture of the carrier is stabilized by introducing the promoting ion on the surface of Pt/Al₂O₃ with vapors of CrO₂Cl₂ or SnCl₄. This is shown by a relatively slower decrease of the specific area and the volume of the pores upon calcination.

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, Pt/Al₂O₃- CrO₂Cl₂ SnCl₄ . .

     

Comparative kinetic and thermodynamic study on the chlorination of V2O5 with CCl4, COCl2 and Cl2

The chlorination kinetics of pure vanadia was studied via isothermal thermogravimetric measurements, with CCl₄, CoCl₂ and Cl₂ as chlorinating agents. At temperatures where chemical control was predominant, apparent activation energies of 77, 48 and 126 kJ: mol^–1 were obtained for chlorination by CCl₄, COCl₄ and Cl₂, respectively. For interpretation of the conversion vs. time curves in the whole conversion range, a non-uniform particle size distribution was assumed, where the reacting solid phase was considered to be composed of thin plates of different thicknesses. With this model, a fairly good correspondence was obtained between the measured and calculated kinetic curves. Selected thermodynamic calculation data on the V₂O₅ + CCl₄, V₂O₅ + COCl₂ and V₂O₅ + Cl₂ systems are presented.

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Zusammenfassung Mittels isothermen Thermogravimetriemessungen wurde die Kinetik der Chlorierung von reinem Vanadiumoxid mit CCl₄, COCl₂ und Cl₂ als Chlorierungsmittel untersucht. Bei Temperaturen mit vorherrschender chemischer Kontrolle wurde für die Chlorierung mit CCl₄, COCl₂ bzw. Cl₂ Bruttoaktivierungsenergien von 77, 48 bzw. 126 kJ/mol erhalten. Zur Interpretation der Konversion-Zeit-Diagramme im gesamten Conversionsbereich wurde eine nichteinheitliche Teilchengrösseverteilung angenommen, namentlich den Bestand der reagierenden Festphase aus dünnen Plättchen unterschiedlicher Dicke. Mit diesem Modell konnte eine recht gute Übereinstimmung zwischen errechneten und ermittelten kinetischen Kurven erhalten werden. Einige thermodynamische Rechenbeispiele für die Systeme V₂O₅ + CCl₄, V₂O₅ + COCl₂ und V₂O₅+Cl₂ wurden gegeben.

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, l₄, l₂ l₂. , l₄, l₂ l₂, 77, 48 126 ·^–1. — , . , . - . V₂O₅+CCl₄, V₂O₅+COCl₂ V₂O₅+Cl₂.

     

Kinetic laws for dehydrogenation of cyclohexane over Pd/C catalysts

A kinetic equation for cyclohexane dehydrogenation at P_O=1.0 MPa has been obtained.

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1,0 .

     

Silylation of porous glass supported platinum catalysts

Effect of silylation with hexamethyldisilazane on adsorption and catalytic properties of porous glass-supported platinum catalysts has been studied. Catalytic activity decreases markedly with an increase in surface coverage by trimethylsilyl groups for all the following reactions examined: hydrogenation of benzene, dehydrogenation of cyclohexane and dehydrocyclization of n-hexane.

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, . , : , -.

     

Ab initio investigation of the electron structure in bis-Cu+ acetylene and vinylidene complexes

[Cu(-C₂H₂)₂]⁺, [Cu(-CCH₂)₂]⁺ and [Cu(-C₂H₂) (-CCH₂]⁺ complexes have been studied by the ab initio double-zeta basis set method. It has been established that all calculated compounds are stable to decomposition into two C₂H₂ molecules and Cu⁺ cation and into one C₂H₂ molecules and the respective monocomplex. Calculation results suggest the possibility of intramolecular acetylene-vinylidene rearrangement in the coordination sphere of Cu⁺.

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ab initio : [Cu(-C₂H₂)₂]⁺, [Cu(-CCH₂)₂]⁺, [Cu(-C₂H₂) (-CCH₂)]⁺. C₂H₂ Cu⁺ C₂H₂ . - Cu⁺.

     

The application of thermoanalytical methods in the investigation of biological substances

The equilibria and thermodynamics of a number of naturally occuring isolated compounds (e.g. proteins, amino acids, carbohydrates) have recently been studied in several laboraties in different temperature ranges, and thermoanalytical methods have been used to study structural changes of biological materials, among them human tissues.In our investigations we succeeded in appling the derivatograph for the assay of glycosaminoglycans and for the characterization of the stability of crosslinked proteins in intact human and animal tissues. By means of this method age-related and pathological changes and repair reactions were studied in various connective and vascular tissues.Other temperature-dependent techniques (DSC, polarizing microscopy) were used successfully in another series of experiments. Alterations in the characteristic order-disorder transition temperatures of human serum lipoproteins could be demonstrated in pathological conditions; the altered physical structure of lipoproteins might give an additional explanation to the assumed mechanism of different metabolic disorders.

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Zusammenfassung Die Gleichgewichte und die Thermodynamik einer Reihe von natürlich vorkommenden isolierten Verbindungen (z. B. Proteine, Aminosäuren, Kohlenhydrate) wurden in verschiedenen Laboratorien in verschiedenen Temperaturbereichen untersucht. Hierbei wurden thermoanalytische Methoden zum Studium der Strukturänderungen von biologischem Material, u. a. von menschlichem Gewebe, eingesetzt.In unseren Untersuchungen gelang es den Derivatographen zur Prüfung von Glycosaminoglycanen und zur Charakterisierung der Stabilität quervernetzter Proteine in intakten menschlichen und tierischen Geweben einzusetzen. Durch diese Methode wurden altersbedingte und pathologische Änderungen sowie Reaktionen zur Wiederherstellung in verschiedenen Binde und Vasculärgeweben studiert.Andere temperaturabhängige Techniken (DSC, Polarisationsmikroskopie) wurden in anderen Versuchsserien mit Erfolg eingesetzt.

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, . , , , , . . , . .

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Plenary lecture     

Observation conditions and thermal stability of O2? on SnO2

A sharp change in the relaxational characteristics of O ₂ ^– anion radicals on SnO₂ is observed under physical adsorption of O₂ molecules in an amount less than 10¹⁶ m^–3. The thermal stability of sites for O ₂ ^– stabilization on SnO₂ is analyzed. Molecular oxygen, forming O₂, is shown to desorb with increasing temperature without participating in reoxidation of the oxide.

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O ₂ ^– SnO₂ O₂ 10¹⁶ M^–2. O ₂ ^– SnO₂. , O₂, O ₂ ^– , .

     

Kinetics and mechanism of the decomposition of pyrite under conventional and quasi-isothermal — quasi-isobaric thermoanalytical conditions

The kinetics and mechanism of the thermal decomposition of pyrite were examined by the method of quasi-isothermal and quasi-isobaric thermogravimetry (Q-TG). It emerged that by means of this technique the overlapping partial processes of the complicated oxidation and decomposition reactions of pyrite can be separated and studied independently from one another. It was found that the partial reactions FeS₂=FeS +S and Fe₂O_3–x(SO₄)_x=Fe₂O₃+SO₃ are endothermic processes taking place quasiisothermally and leading to equilibrium, while the oxidation FeS+O₂=Fe₂O_3–x(SO₄)_x is an exothermic process which takes place in an oscillating manner in a rather broad temperature interval.

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Zusammenfassung Autoren untersuchten die Kinetik und den Mechanismus der thermischen Zersetzung von Pyrit durch quasi-isotherme und quasi-isobare Thermogravimetrie (Q-TG). Es stellte sich heraus, daß sich überlagernde Teilprozesse der komplizierten Oxydations- und Zersetzungsprozesse von Pyrit mit Hilfe dieser Technik absondern und unabhängig voneinander untersuchen lassen. Es wurde festgestellt, daß die Teilreaktionen FeS₂=FeS+S und Fe₂O_3–x(SO₄)_x=Fe₂O₃+SO₃ endotherme Prozesse sind, die quasi-isotherm verlaufen und zu einem Gleichgewicht führen, während die Oxydation FeS+O₂=Fe₂O_3–x(SO₄)_x ein exothermer Prozeß ist, der oszillierend in einem ziemlich breiten Temperaturintervall verläuft.

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(Q-) . . , FeS₂=FeS+S Fe₂O_3–x(S₂O₄)_x=Fe₂O₃+SO₃ , . FeS+O₂ =Fe₂O_3–x(SO₄)_x , .

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The authors thank Prof. E. Pungor for valuable discussions, and Mrs. M. Kiss and Miss I. Fabian for their technical assistance.     

Estimate of acid dissociation constants by the interacting bonds method exemplified by aquacomplexes of Pt(II) and Pt(IV)

Acid dissociation constants of aqua complexes of Pt(II) and Pt(IV) have been estimated by the interacting bonds method. Calculation and experiment are compared.

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Pt(II) Pt(IV). .

     

Properties of template-free synthetic (B, Al) pentasil type zeolites

Template-free synthetic, boron-containing pentasil type zeolites exhibit structural and catalytic properties similar to those of SABO zeolites made in the presence of n-propylamine.

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, , , SABO, -.